Starch film and method for manufacturing starch foam

ABSTRACT

A biodegradable starch film is provided. The biodegradable starch film includes a starch which is cross-linked by means of a cross-linking agent. The cross-linking agent comprises glycidyl methacrylate 2,3-epoxypropyl methacrylate (GMA), octenyl succinyl anhydride (OSA), or dodecyl succinic anhydride (DDSA) or combinations thereof. The cross-linking agent is 1 to 10 weight parts based on the starch of 100 weight parts. Furthermore, a method for manufacturing starch foam is also provided.

This application is a Continuation-In-Part of pending U.S. patentapplication Ser. No. 12/118,693 filed May, 10, 2008 and entitled“Methods for Manufacturing Starch Foam”, which claims priority of TaiwanPatent Application No. 96150509, filed on Dec. 27, 2007, the entirety ofwhich is incorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a starch film and a method for manufacturing astarch foam.

2. Description of the Related Art

The Waste Electrical and Electronic Equipment (WEEE) Directive (EuropeanCommunity directive 2002/96/EC) and the Restriction of HazardousSubstance (RoHS) Directive (European Community directive 2002/95/EC)have been published by the European Union (EU) since 2003, and obligesEU member states to transpose its provisions into national law forsetting collection, recycling and recovery targets for all types ofelectrical goods. As of July 2006, the maximum weight for the substancesof lead, mercury, cadmium, chromium (VI), polybrominated biphenyls (PBB)and polybrominated diphenyl ethers (PBDE) are prohibited by the RoHSDirective. If an electronic equipment has these substances which exceedthe limit, the electronic equipment will not be allowed into EU memberstates. Manufacturing products in consideration of environmentalfriendliness (or so-called “green products’) is a major subject for themanufacturing industry. For green products, all parts of a product mustconform to the proper directives. As such, manufacturing techniquesspecifically geared toward green products have increased in demand dueto environmental friendliness.

With conventional plastics seldom being hard to self-decompose, theycause environmental issues when discarded. Thus, degradable plasticshave been imported, researched and manufactured in many countries.Recently, developed countries have increased research for eco-materials,such as environmentally friendly materials. Meanwhile, cheap materials,such as PVC and EPS, are the main packaging materials previously used.Since PVC contains chlorine, it causes an environment issue during itswhole life cycle, such as during production, use, and when discarded.PVC is called a “poison plastic” by Greenpeace International, and isdeemed not fit for environmental demands. Thus, PVC has been substitutedby polyolefin. However, no suitable material has been developed, thatwould feasibly be a substitute for ESP. Thus, increased methods formanufacturing and modeling materials which can be popularly or speciallyapplied should be developed to meet demands for lower costs, recyclingcapabilities and environmental friendliness.

For example, cellulose, starch and chitosan are natural materials whichcan be decomposed in nature. In particular, starch is one of the bestbiodegradable raw materials due to its good processability andbiodegradability.

Starch is a hydrophilic polymer and the hydroxyl groups therein reactwith the hydrogen bond of water. Thus, plastics formed of pure starchare not suitable for an environment with moisture. To address thisissue, one solution is to mix the starch with hydrophobic polymers toimprove water resistance. However, the compositions have shortcomings asperforming uniform mixing is difficult and combining of the starch andthe hydrophobic polymers may be weak.

Therefore, a starch composition capable of addressing the above issuesis desired.

BRIEF SUMMARY OF INVENTION

A detailed description is given in the following embodiments withreference to the accompanying drawings.

The present invention provides an embodiment of a biodegradable starchfilm. The biodegradable starch film includes a starch which iscross-linked by means of a cross-linking agent. The cross-linking agentincludes glycidyl methacrylate 2,3-epoxypropyl methacrylate (GMA),octenyl succinyl anhydride (OSA), or dodecyl succinic anhydride (DDSA)or combinations thereof. The cross-linking agent is 1 to 10 weight partsbased on the starch of 100 weight parts.

The present invention provides another embodiment of a method formanufacturing starch foam. The method includes modifying a starch by across-linking agent, wherein the cross-linking agent includes glycidylmethacrylate 2,3-epoxypropyl methacrylate (GMA), octenyl succinylanhydride (OSA), or dodecyl succinic anhydride (DDSA) or combinationsthereof. The cross-linking agent is 1 to 10 weight parts based on thestarch of 100 weight parts. The modified starch is mixed with anucleating agent and a foaming agent to form a foamable mixture. Thefoamable mixture is foamed to form a foam.

BRIEF DESCRIPTION OF DRAWINGS

The present invention can be more fully understood by reading thesubsequent detailed description and examples with references made to theaccompanying drawings, wherein:

FIGS. 1( a) and 1(b) show the SEM images of the modified starch film inExample 1 and the non-modified starch film in Comparative Example 1,respectively.

FIG. 2 illustrates a schematic view showing a biodegradation test systemaccording to an embodiment of the invention.

DETAILED DESCRIPTION OF INVENTION

A starch film and a method for manufacturing a starch foam of thepresent invention are described in detail as follows. The starch filmmay comprise a starch modified by a cross-linking agent. The starch mayinclude a cereal or a root crop. The cereal may include rice, wheat,corn or other natural cereal plants. The root crop may include cassava,sweet potato, potato or other natural root crop plants. In addition tothe cereal and the root crop, the starch may also include any planthaving starch elements.

The starch has at least two hydroxyl groups capable of reacting with thecross-linking agent. Thus, by using the cross-linking agent, thehydroxyl groups of the starch may be transformed to hydrophobic groupsresulting in improved water resistance of the modified starch. Forexample, the starch may be preferably modified by an epoxy cross-linkingagent or an acid anhydride cross-linking agent, wherein the carbonnumbers of the cross-linking agent are between 5 and 20 weight parts,preferably between 5 and 10 weight parts based on the starch of 100weight parts. In the present embodiment, the cross-linking agent may beglycidyl methacrylate 2,3-epoxypropyl methacrylate (GMA), octenylsuccinyl anhydride (OSA), or dodecyl succinic anhydride (DDSA) orcombinations thereof. The cross-linking agent is 1 to 10 weight partsbased on the starch of 100 weight parts.

Furthermore, the hydrogen bonds between the starches may be replacedwith covalent bonds by means of the cross-linking agent such thatstronger bonding (e.g., ester bond) and longer paths may be formedbetween the starches. The starches are highly cross-linked. Thus, thewater penetrating path increases in length and the water vaportransmission rate is reduced.

For example, the starch film may have a thickness of between 0.02 and0.10 mm. In one embodiment, the starch film may have a water vaportransmission rate of between 5.2*10⁻³ and 9.8*10⁻³ gm⁻²s⁻¹, and may havea water vapor permeability of between 10.5*10⁻¹¹ and 19.6*10⁻¹¹gm⁻²s⁻¹Pa⁻¹.

In addition, a starch foam may be formed from the modified starch. Thestarch foam may include the modified starch, a nucleating agent, and afoaming agent. In one embodiment, the nucleating agent may includecalcium carbonate, calcium hydroxide, silicate or other suitablenucleating agents. The nucleating agent is 0.1 to 20 weight parts basedon the modified starch of 100 weight parts. The foaming agent mayinclude water, carbon dioxide, nitrogen, oxygen, air, alcohol or othersuitable foaming agents. The foaming agent is 0.1 to 20 weight partsbased on the modified starch of 100 weight parts.

In addition to the modified starch, the nucleating agent, and thefoaming agent, the starch foam may further include an additive and/or aplasticizing agent. The additive may include polyvinyl alcohol or othersuitable additives. The additive is 0 to 50 weight parts based on themodified starch 100 weight parts. The plasticizing agent may includeglycerol or other suitable plasticizing agents. The plasticizing agentis 0 to 30 weight parts based on the modified starch of 100 weightparts.

The starch foam is formed by the following steps: (a) the weightedmodified starch and the weighted nucleating agent are put into a highspeed mixer for mixing with a high speed of 3000 rpm for 1 minute andthen left standing for 5 minutes, (b) the foaming agent, orappropriately the additive, the plasticizing agent and the cross-linkingagent are put into the high speed mixture for mixing with a high speedof 3000 rpm for 3 minutes and then left standing for 5 minutes, mixingwith a high speed of 3000 rpm for 3 minutes and then left standing for 5minutes, and mixing with a high speed of 3000 rpm for 3 minutes and thenleft standing for 10 minutes, in sequence. Therefore the mixture ismixed to form the foamable mixture.

Next, the foamable mixture is foamed to form the foam. The foaming stepincludes mold press foaming or extrusion foaming. The mold compressionfoaming step includes pressing the foamable mixture, weighted by theelectronic control system, into a mold by a hydraulic press system, andthen mold compression foaming the foamable mixture at a pressure of20-100 kg/cm² and a temperature of 120-180° C. to form the foam. Theextrusion foaming step includes kneading the foamable mixture into grainby a twin-screw extruder, and then extrusion foaming the grain foamablemixture to form the foam by a single-screw extruder at a temperature of120-180° C.

The following description is of the best-contemplated mode of carryingout the invention. This description is made for the purpose ofillustrating the general principles of the invention and should not betaken in a limiting sense. The scope of the invention is best determinedby reference to the appended claims.

Example 1

A corn starch-aqueous alcohol suspension was prepared and 3 weight partsof glycidyl methacrylate 2,3-epoxypropyl methacrylate (GMA) (based on100 weight parts of the corn starch) was added to the suspension. Thesuspension was stirred under N₂ at room temperature for 3 hours. Then,the suspension was stirred at 95° C. for 1 hour and graduallytransformed to a gel. Finally, the gel was placed in a petri dish anddried at 60° C. for 3 hours to obtain a GMA modified starch film. Thethickness, moisture content, water vapor transmission rate and watervapor permeability of the GMA modified starch film is shown in Table 1.

Example 2

A corn starch-aqueous alcohol suspension was prepared and 5 weight partsof octenyl succinyl anhydride (OSA) (based on 100 weight parts of thecorn starch) was added to the suspension. The pH value of the suspensionwas adjusted to about 8 and the suspension was stirred at roomtemperature for 24 hours. Then, the suspension was stirred at 80° C. for1 hour and then at 95° C. for 1 hour. The suspension was graduallytransformed to a gel. Finally, the gel was placed in a petri dish anddried at 60° C. for 3 hours to obtain an OSA modified starch film. Thethickness, moisture content, water vapor transmission rate and watervapor permeability of the OSA modified starch film is shown in Table 1.

Example 3

A corn starch-aqueous alcohol suspension was prepared and its pH valuewas adjusted to 2.5. 7 weight parts of dodecyl succinic anhydride (DDSA)(based on 100 weight parts of the corn starch) was added to thesuspension. The pH value of the suspension was adjusted to about 8 andthe suspension was stirred at 35° C. for 3 hours. Then, the suspensionwas stirred at 80° C. for 1 hour and then at 95° C. for 1 hour. Thesuspension was gradually transformed to a gel. Finally, the gel wasplaced in a petri dish and dried at 60° C. for 3 hours to obtain a DDSAmodified starch film. The thickness, moisture content, water vaportransmission rate and water vapor permeability of the DDSA modifiedstarch film is shown in Table 1.

Comparative Example 1

A corn starch-aqueous alcohol suspension was prepared. Then, thesuspension was stirred at 80° C. for 1 hour and then at 95° C. for 10minutes. The suspension was gradually transformed to a gel. Finally, thegel was placed in a petri dish and dried at 60° C. for 3 hours to obtaina starch film. The thickness, moisture content, water vapor transmissionrate and water vapor permeability of the starch film is shown in Table1.

TABLE 1 Characteristics of the starch films in Examples 1-3 andComparative Examples 1-3 Water vapor Water vapor Moisture transmissionpermeability Thickness content rate (10⁻³ * (10⁻¹¹ * (mm) (%) gm⁻²s⁻¹)gm⁻²s⁻¹Pa⁻¹) Example 1 (GMA) 0.055 3.4 6.5 11.2 Example 2 (OSA) 0.0656.8 7.2 14.6 Example 3 (DDSA) 0.06 4.6 6.9 12.9 Comparative 0.065 9.27.8 15.8 Example 1 (non- modified)

As shown in Table 1, each of the modified starch films in Examples 1-3had a water content much lower than the non-modified starch film inComparative Example 1. In particular, the GMA modified starch film inExample 1 had a moisture content as low as 3.4% which is only about ⅓ ofthat of the non-modified starch film. Furthermore, the water vaportransmission rate and the water vapor permeability of each of themodified starch films in Examples 1-3 were also much lower than that ofthe non-modified starch film. From these results, it can be suggestedthat the starch film modified by the cross-linking agent may lead to thestarch film being more hydrophobic and having longer paths for waterpenetration. Thus, the water resistance of the modified starch film wassignificantly improved.

FIGS. 1( a) and 1(b) show the SEM images of the modified starch film inExample 1 and the non-modified starch film in Comparative Example 1,respectively. As shown in FIG. 1( a), it can be seen that block shapedstructures of the modified starches were formed from the small starchparticles shown in FIG. 1( b) after cross-linking. The longer pathsbetween the starches for water penetration were clearly shown in the SEMimages.

Examples 4-6

Powdery rice, calcium carbonate of the nucleating agent, glycerol of theplasticizing agent, water of the foaming agent, and GMA, OSA, DDSA ofthe cross-linking agent with ratios as shown in Tables 2˜4,respectively, were well mixed to form a foamable mixture. The foamablemixture, weighted by using the electronic control system, was thenpressed into the mold by using the hydraulic press system. Next, thefoamable mixture was mold compression foamed to form the foam at apressure of 20-100 kg/cm² and temperature of 120-180° C. The results ofthe Examples 4˜6 are shown in Table 9.

Comparative Examples 2˜4

Powdery rice, calcium carbonate of the nucleating agent, glycerol of theplasticizing agent, water of the foaming agent, and ethylene dialdehydemonomer, acetic anhydride monomer, methyl methacrylate monomer of thecross-linking agent with ratios as shown in Tables 5˜7, respectively,were well mixed to form a foamable mixture. The foamable mixture,weighted by using the electronic control system, was then pressed intothe mold by using the hydraulic press system. Next, the foamable mixturewas mold compression foamed to form the foam at a pressure of 20˜100kg/cm² and temperature of 120-180° C. The results of the ComparativeExamples 2-4 are shown in Table 9.

Comparative Example 5

Powdery rice, calcium carbonate of a nucleating agent, glycerol of aplasticizing agent, and water of a foaming agent were well mixed withratios as shown in Table 8 to form a foamable mixture. The foamablemixture, weighted by the electronic control system, was pressed into themold by using the hydraulic press system. Next, the foamable mixture wasmold compression foamed form the foam at a pressure of 20-100 kg/cm² andtemperature of 120-180° C. The result of the Comparative Example 5 isshown in Table 9.

TABLE 2 The components of the mixture for the Example 4 component weight(powdery) rice 100 calcium carbonate 8 glycerol 5 GMA 5 water 30

TABLE 3 The components of the mixture for the Example 5 component weight(powdery) rice 100 calcium carbonate 8 glycerol 5 OSA 5 water 30

TABLE 4 The components of the mixture for the Example 6 component weight(powdery) rice 100 calcium carbonate 8 glycerol 5 DDSA 5 water 30

TABLE 5 The components of the mixture for the Comparative Example 2component weight (powdery) rice 100 calcium carbonate 8 glycerol 5Ethylene dialdehyde 5 monomer water 30

TABLE 6 The components of the mixture for the Comparative Example 3component weight (powdery) rice 100 calcium carbonate 8 glycerol 5Acetic anhydride monomer 5 water 30

TABLE 7 The components of the mixture for the Comparative Example 4component weight (powdery) rice 100 calcium carbonate 8 glycerol 5Methyl methacrylate 5 monomer water 30

TABLE 8 The components of the mixture for the Comparative Example 5component weight (powdery) rice 100 calcium carbonate 8 glycerol 5 water30

TABLE 9 Characteristics of EPS, and foams formed by the method accordingto the Examples 4~6 and Comparative Examples 2~5 Comparative ComparativeComparative Comparative Example 4 Example 5 Example 6 Example 2 Example3 Example 4 Example 5 EPS density (g/cm³) 0.182 0.153 0.178 0.222 0.2320.242 0.213 0.021 pH value 6.8 6.5 6.7 6.3 6.2 6.8 7.0 7.2 dimensionchange (%) +0.3 +0.3 +0.3 +0.5 +0.5 +0.5 +0.6 +0.4 compressive strength5.73 4.12 4.86 3.18 3.26 3.47 2.82 2.18 (kgf/cm²) biodegradation(%/day) >70/45 >70/45 >70/45 >70/45 >70/45 >70/45 >70/45 <10/180

The experimental results, illustrated in Table 9, show that thecompressive strength of the foams formed by the methods according to theexamples is stronger than that of the dialdehyde monomer, anhydridemonomer, and acrylic monomer. Thus, the foams formed by the methodsaccording to the examples withstood higher stress even with lessdensity. Biodegradation tests were performed according to the CNS144321national standard. The EPS and the foams of the Examples 4˜6 andComparative Examples 2˜5 were tested for aerobic biodegradation and thedisintegration, and analyzed for carbon dioxide liberation, in a muckenvironment by the method as shown in FIG. 2. An air 1 was flowed into ade-carbon dioxide system 7 containing a sodium hydroxide solution 6 toform an air without carbon dioxide 2. The air without carbon dioxide 2was flowed into a muck container 8 containing a test compound 5, and wasdecomposed by the test compound 5 to form an air with carbon dioxide 3.The air with carbon dioxide 3 was tested for a quantity of carbondioxide by a carbon dioxide test system 9. The test foams were put in amuck container 8 at a stable temperature of 58±2° C. and isolated fromvapor that may affect organisms. The test was designed for theconversion ratio of the carbon elements of the test foams into thecarbon dioxide. The duration of the test was generally 180 days. Thebiodegradation of the foams, formed by the methods according to theexamples 4, 5, and 6, were 70% in the duration of only 45 days. Thus,the foams were defined as being biodegradable according to the CNS144321 national standard. However, the biodegradation of theconventional EPS was lower than 10% in the duration of 180 days, thusshowing that the conventional EPS does affect the global environment.Since the foams of the invention are manufactured using the cereal orthe root crop of natural plants by the method according to theinvention, the foams of the invention do not cause environmentalpollution issues.

While the invention has been described by way of example and in terms ofthe preferred embodiments, it is to be understood that the invention isnot limited to the disclosed embodiments. To the contrary, it isintended to cover various modifications and similar arrangements (aswould be apparent to those skilled in the art). Therefore, the scope ofthe appended claims should be accorded the broadest interpretation so asto encompass all such modifications and similar arrangements.

1. A biodegradable starch film, comprising: a starch which iscross-linked by means of a cross-linking agent, wherein thecross-linking agent comprises glycidyl methacrylate 2,3-epoxypropylmethacrylate (GMA), octenyl succinyl anhydride (OSA), or dodecylsuccinic anhydride (DDSA) or combinations thereof, wherein thecross-linking agent is 1 to 10 weight parts based on the starch of 100weight parts.
 2. The biodegradable starch film as claimed in claim 1,wherein the starch comprises a cereal, or a root crop.
 3. Thebiodegradable starch film as claimed in claim 2, wherein the cerealincludes rice, wheat or corn.
 4. The biodegradable starch film asclaimed in claim 1, which has a thickness of between 0.02 and 0.10 mm.5. The biodegradable starch film as claimed in claim 1, which has amoisture content of between 2 and 15%.
 6. The biodegradable starch filmas claimed in claim 1, which has a water vapor transmission rate ofbetween 5.2*10⁻³ and 9.8*10⁻³ gm⁻²s⁻¹.
 7. The biodegradable starch filmas claimed in claim 1, which has a water vapor permeability of between10.5*10⁻¹¹ and 19.6*10⁻¹¹ gm⁻²s⁻¹Pa⁻¹.
 8. A method for manufacturingstarch foam, comprising: modifying a starch by a cross-linking agent,wherein the cross-linking agent comprises glycidyl methacrylate2,3-epoxypropyl methacrylate (GMA), octenyl succinyl anhydride (OSA), ordodecyl succinic anhydride (DDSA) or combinations thereof, and thecross-linking agent is 1 to 10 weight parts based on the starch of 100weight parts; mixing the modified starch with a nucleating agent and afoaming agent to form a foamable mixture; and foaming the foamablemixture to form a foam.
 9. The method as claimed in claim 8, wherein thestarch comprises a cereal, or a root crop.
 10. The method as claimed inclaim 9, wherein the cereal includes rice, wheat or corn.
 11. The methodas claimed in claim 8, wherein the nucleating agent comprises calciumcarbonate, calcium hydroxide or silicate.
 12. The method as claimed inclaim 8, wherein the foaming agent comprises water, carbon dioxide,nitrogen, oxygen, air or alcohol.
 13. The method as claimed in claim 8,wherein the modified starch further mixes with an additive, aplasticizing agent or combinations thereof.
 14. The method as claimed inclaim 13, wherein the additive comprises polyvinyl alcohol.
 15. Themethod as claimed in claim 13, wherein the plasticizing agent comprisesglycerol.
 16. The method as claimed in claim 8, wherein the foaming stepcomprises mold press foaming or extrusion foaming.
 17. The method asclaimed in claim 16, wherein the mold press foaming and the extrusionfoaming are performed at a temperature of 120-180° C.
 18. The method asclaimed in claim 8, wherein the starch foam has a biodegradation lowerthan 10% in a duration of 180 days.